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EP0107780B1 - Fluoran compounds - Google Patents

Fluoran compounds Download PDF

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Publication number
EP0107780B1
EP0107780B1 EP83109287A EP83109287A EP0107780B1 EP 0107780 B1 EP0107780 B1 EP 0107780B1 EP 83109287 A EP83109287 A EP 83109287A EP 83109287 A EP83109287 A EP 83109287A EP 0107780 B1 EP0107780 B1 EP 0107780B1
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EP
European Patent Office
Prior art keywords
fluoran
product
methoxy
mec
anilino
Prior art date
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Expired
Application number
EP83109287A
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German (de)
French (fr)
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EP0107780A3 (en
EP0107780A2 (en
Inventor
Mitsutoshi C/O Hodogaya Chemical Co. Ltd. Anzai
Masahiko Hodogaya Chemical Co. Ltd. Yamaguchi
Michihiro C/O Hodogaya Chemical Co. Ltd. Gonda
Mikiko C/O Hodogaya Chemical Co. Ltd. Kanasugi
Toshio Hodogaya Chemical Co. Ltd. Obara
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Hodogaya Chemical Co Ltd
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Hodogaya Chemical Co Ltd
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Priority claimed from JP17103982A external-priority patent/JPS5962666A/en
Priority claimed from JP809483A external-priority patent/JPS59135254A/en
Application filed by Hodogaya Chemical Co Ltd filed Critical Hodogaya Chemical Co Ltd
Publication of EP0107780A2 publication Critical patent/EP0107780A2/en
Publication of EP0107780A3 publication Critical patent/EP0107780A3/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/20—Duplicating or marking methods; Sheet materials for use therein using electric current
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/10—Spiro-condensed systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24835—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including developable image or soluble portion in coating or impregnation [e.g., safety paper, etc.]

Definitions

  • the present invention relates to novel fluoran compounds. More particularly, the invention relates to 2- substituted amino-3-alkoxy-6-di-substituted aminofluoran compounds which are useful as color precursors for heat sensitive record sheets or electrical heat sensitive record sheets.
  • Example E discloses in Example E a fluoran compound having an alkoxy group of the 3-position.
  • FR-A-2 230 632 discloses a wide range of fluoran compounds and heat sensitive recording sheets, therein and fluoran compounds are used.
  • fluoran compounds have been disclosed in Japanese Examined Patent Publications No. 2406/ 1973, No. 43296/1973, No. 32767/1974 and No. 23204/1976, and Japanese Unexamined Patent Publication No. 34526/1974. These fluoran compounds are used as color precursors for heat sensitive record sheets or electrical heat sensitive record sheets.
  • heat sensitive record sheets wherein these fluoran compounds are used as color precursors have various drawbacks, for instance, in the developed color density, the initial color density, the color-development initiation temperature and the gradient for color-development. Therefore, they cannot provide adequate properties required for heat sensitive record sheets.
  • 2-anilino-3-methyl-6-diethylamino-fluoran disclosed in the above-mentioned Japanese Examined Patent Publications, tends to undergo partial color development during the preparation of heat sensitive record sheets, whereby the initial color density of the record sheets tends to be high.
  • the initial color density is low, but the color-development initiation temperature is too high and the gradient for the color development is inadequate.
  • 2-anilino-3-methyl-6-N-methyl-N-cyclohexylamino-fluoran does not provide an adequate gradient for color development.
  • the gradient for color-development means a rising of a curve in a diagram of color density-color development temperature curve given by plotting color densities on the ordinate and color-development temperatures on the abscissa as a value given by multiplying by 100 the value of tan 6 in the maximum slant of the curve.
  • the present inventors have conducted extensive researches for fluoran compounds to be used for heat sensitive record sheets which have no substantial self-color development, a high developed color density, a low color-development initiation temperature and a high gradient for color-development, and have finally found that 2-substituted amino-3-alkoxy-6-di-substituted aminofluoran compounds have excellent properties to satisfy the above requirements.
  • the present invention provides fluoran compounds represented by general formula: where each of R, and R 2 is a C,-C 4 alkyl group, a cyclohexyl group or an optionally substituted phenyl group as defined in claim 1, or R, and R 2 may form together with N a saturated ring, R 3 is a benzyl or phenyl group which may be substituted by a methyl group, an ethyl group or a halogen atom, and R 4 is a C l -C 4 alkyl group, provided that when R, and R 2 are ethyl and R 3 is phenyl, R 4 is not a methyl group.
  • the present invention also provides a heat sensitive record sheet which comprises a coated layer comprising a fluoran compound represented by the above general formula I.
  • the fluoran compounds represented by the general formula I according to the present invention are colorless or slightly colored solids which are stable in air and which, when brought in contact with an acidic substance, immediately form coloring agents having a dark black color.
  • the developed coloring agents have excellent storage stability and are therefore quite useful.
  • the fluoran compounds represented by the general formula I according to the present invention may be prepared by following method (1), (2) or (3).
  • the method (1) is preferred.
  • N - benzyl - 2,4 - dimethoxyaniline N - phenyl - 2,4 - dimethoxyaniline, N - (2 - methylphenyl) - 2,4 - dimethoxyaniline, N - (4 - methylphenyl) - 2,4 - dimethoxyaniline, N - (2 - chlorophenyl) - 2,4 - dimethoxyaniline, N - (4 - chlorophenyl) - 2,4 - dimethoxyaniline, N -benzyl -4 -hydroxy -2 -methoxyaniline, N -phenyl -4 -hydroxy -2 - methoxyaniline, N - phenyl - 2,4 - diethoxyaniline, N - (2 - methylphenyl) - 2,4 - diethoxyaniline, N - (4 - methylphenyl) - 2,4 - diethoxyaniline, N - (4 -
  • substituted benzylchloride or the substituted benzyl bromide to be used in the present invention there may be mentioned benzylchloride, benzylbromide, 2-chlorobenzylchloride, 2-chlorobenzylbromide, 3-chlorobenzylchloride, 4-chlorobenzylchloride, 2-methylbenzylchloride, 4-methylbenzylchloride, 3-methylbenzylchloride and 2-methylbenzylbromide.
  • substituted bromobenzene or substituted chlorobenzene there may be mentioned 2-bromochlorobenzene, o-dichlorobenzene, 3-bromochlorobenzene, 4-bromochlorobenzene, bromobenzene, 2-bromotoluene, 4-bromotoluene or 3-bromotoluene.
  • concentrated sulfuric acid As the condensing agent to be used in the present invention, there may be mentioned concentrated sulfuric acid, acetic acid anhydride, phosphoric acid, polyphosphoric acid, phosphorus oxychloride and zinc chloride. From the practical point of view, it is preferred to use concentrated sulfuric acid which serves as a solvent for a benzophenone compound represented by the above general formula III and at the same time serves as a condensing agent.
  • this product had ⁇ max at 439 nm (a molecular extinction coefficient (hereinafter referred to simply as "MEC"): 1.42 x 10 4 ) and at 583 nm (MEC: 3.91 x 10 4 ) as measured in 95% acetic acid.
  • MEC molecular extinction coefficient
  • N-benzyl-2,4-dimethoxyaniline used as a starting material was prepared in the following manner.
  • the reaction mixture was poured into 1 liter of water and extracted with 500 m of toluene.
  • the toluene layer was washed with water, concentrated and purified by distillation under reduced pressure, whereby 40.9 g of N-benzyl-2,4-dimethoxyaniline was obtained.
  • the product was a liquid having a boiling point of from 166 to 168°C 266 PLa (2 mmHg).
  • the product had ⁇ max at 443 nm (MEC: 1.55 x 10 4 ) and at 587 nm (MEC: 3.94 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned blackish purple.
  • the product had ⁇ max at 451 nm (MEC; 1.52 x 10 4 ) and at 593 nm (MEC: 3.29 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • the product had ⁇ max at 450 nm (MEC: 1.63 x 10 4 ) and at 593 nm (MEC: 3.45 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish-black.
  • the product had ⁇ max at 453 nm (MEC: 1.82 x 10 4 ) and at 595 nm (MEC: 3.19 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • the product had ⁇ max at 441 nm (MEC: 1.40 x 10 4 ) and at 586 nm (MEC: 3.18 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
  • the N-(2-methylphenyl)-2,4-dimethoxyaniline used as a starting material was prepared in the same manner as in Example 4 by using N-acetyl-2,4-dimethoxyaniline and 2-bromotoluene as the starting materials.
  • the boiling point of the N-(2-methylphenyl)-2,4-dimethoxyaniline was from 172 to 175°C/266 Pa (2 mmHg).
  • the product had ⁇ max at 444 nm (MEC: 1.57 x 10 4 ) and at 588 nm (MEC: 3.64 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
  • the product had ⁇ max at 453 nm (MEC: 1.40 x 10 4 ) and at 595 nm (MEC: 2.58 x 10 4 ) as measured in 95% aceticacid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned black.
  • the N-(4-methylphenyl)-2,4-dimethoxyaniline used as a starting material was prepared in the same manner as in Example 4 by using N-acetyl-2,4-dimethoxyaniline and 4-bromotoluene as the starting materials.
  • the boiling point of the N-(4-methylphenyl)-2,4-dimethoxyaniline was from 173 to 175°C/266 Pa (2 mmHg).
  • the product had ⁇ max at 455 nm (MEC: 1.65 x 10 4 ) and at 600 nm (MEC: 3.14 x 10 4 ) as measured in 95% acetics acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • the product had ⁇ max at 437 nm (MEC: 1.29 x 10 4 ) and at 577 nm (MEC: 3.63 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned dark red.
  • the N-(2-chlorophenyl)-2,4-dimethoxyaniline used as a starting material was prepared in the same manner as in Example 4 by using N-acetyl-2,4-dimethoxyaniline and 2-bromochlorobenzene as the starting materials.
  • the N-(2-chlorophenyl)-2,4-dimethoxyaniline was an oil having a boiling point of from 170 to 177°C/266 Pa (2 mmHg).
  • the product had ⁇ max at 440 nm (MEC: 1.30 x 10 4 ) and at 580 nm (MEC: 3.78 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned dark red.
  • the product had ⁇ max at 449 nm (MEC: 1.34 x 10 4 ) and at 587 nm (MEC: 2.95 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
  • the N-(4-chlorophenyl)-2,4-dimethoxyaniline used as a starting material was prepared in the same manner as in Example 4 by using N-acetyl-2,4-dimethoxyaniline and 4-bromochlorobenzene as the starting materials.
  • the N-(4-chlorophenyl)-2,4-dimethoxyaniline was an oil having a boiling point of from 178 to 180°C/266 Pa (2 mmHg).
  • the product had ⁇ max at 449 nm (MEC: 1.46 x 10 4 ) and at 590 nm (MEC: 3.36 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • the product had ⁇ max at 452 nm (MEC: 1.44 x 10 4 ) and at 593 nm (MEC: 2.93 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact in which silica gel, the product readily underwent color-development and turned bluish black.
  • the N-phenyl-2,4-diethoxyaniline used as starting material was prepared in the following manner.
  • the toluene layer was washed with water, separated by liquid separation, concentrated and then purified by distillation under reduced pressure, whereby 54 g of oily N-phenyl-2,4-di-ethoxyaniline was obtained.
  • the boiling point of this product was from 180 to 185°C/399 Pa (3 mmHg).
  • the product had ⁇ max at 453 nm (MEC: 1.48 x 10 4 ) and at 597 nm (MEC: 3.17 x 10°) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • the product had ⁇ max at 452 nm (MEC: 1.47 x 10 4 ) and at 597 nm (MEC: 3.16 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • the product had ⁇ maX at 453 nm (MEC: 1.92 x 10 4 ) and at 595 nm (MEC: 3.42 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • the N-(2-methylphenyl)-2,3-diethoxyaniline used as a starting material was prepared in the same manner as in Example 16 by using N-acetyl-2,4-diethoxyaniline and 2-bromotoluene as the starting materials.
  • the boiling point of the N-(2-methylphenyl)-2,4-diethoxyaniline was from 170 to 172°C/67 Pa (0.5 mmHg).
  • the product had ⁇ max at 444 nm (MEC: 1.49 x 10 4 ) and at 589 nm (MEC: 3.63 x 10 4 ) as measured in 95% acetic acid.
  • A. solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
  • the N-(4-methylphenyl)-2,4-diethoxyaniline used as a starting material was prepared in the same manner as in Example 16 by using N-acetyl-2,4-diethoxyaniline and 4-bromotoluene as the starting materials.
  • the boiling point of the N-(4-methylphenyl)-2,4-diethoxyaniline was from 195 to 197°C/399 Pa (3 mmHg).
  • the product had ⁇ max at 454 nm (MEC: 1.57 x 10 4 ) and at 597 nm (MEC: 3.14 x 10°) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
  • the product had ⁇ max at 459 nm (MEC: 1.84 x 10 4 ) and at 601 nm (MEC: 2.92 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, and the product readily underwent color-development and turned greenish black.
  • the product had ⁇ max at 448 nm (MEC: 1.55 x 10 4 ) and at 589 nm (MEC: 3.50 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • the N-(4-chlorophenyl)-2,4-diethoxyaniline used as a starting material was prepared in the same manner as in Example 16 by using N-acetyl-2,4-diethoxyaniline and 4-bromochlorobenzene as the starting materials.
  • the N-(4-chlorophenyl)-2,4-diethoxyaniline had a boiling point of from 188 to 190°C/67 Pa (0.5 mmHg).
  • the product had ⁇ max at 449 nm (MEC: 1.39 x 10 4 ) and at 590 nm (MEC: 3.48 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • the product had ⁇ max at 453 nm (MEC: 1.68 x 10 4 ) and at 593 nm (MEC: 3.33 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • the product had ⁇ max at 454 nm (MEC: 1.66 x 10 4 ) and at 591 nm (MEC: 3.13 x 10 4 ) as measured in 95% acetic acid.
  • a solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • Both slurries were mixed, and the mixture was uniformly dispersed and mixed at room temperature for 1 hour, whereby a slurry mixture was prepared.
  • This slurry mixture was coated on one surface of a normal paper of 50 g/m 2 by means of a wire bar coater (wound wire: 0.35 mm in diameter) in an amount of the coated compound being 1.5 g/m 2 of the paper.
  • the coated paper was dried in air at room temperature, whereby a heat sensitive record sheet having a substantially colorless heat sensitive layer was obtained.
  • This heat sensitive record sheet will be referred to as No. a.
  • heat sensitive record sheets No. b to No. o were prepared by using Compounds No. B to No. O.
  • Both slurries were mixed, and the mixture was uniformly dispersed and mixed at room temperature for 1 hour, whereby a slurry mixture was prepared.
  • This slurry mixture was coated on one surface of a normal paper of 50 g/m 2 by means of a wire bar coater (wound wire: 0.35 mm in diameter) in an amount of the coated compound being 1.5 g/m 2 of the paper.
  • the coated paper was dried in air at room temperature, whereby a heat sensitive record sheet having a substantially colorless heat sensitive layer was obtained.
  • This heat sensitive record sheet will be referred to as No. p.
  • heat sensitive record sheets No. q to No. ab were prepared by using Compounds No. Q to No. AB.
  • heat sensitive record sheets No. ac, No. ad and No. ae were prepared in the same manner as above by using known 2-anilino-3-methyl-6-diethylamino-fluoran (Compound No. AC) 2-anilino-3-methyl-6-N-methyl-N-cyclohexylamino-fluoran (Compound No. AD) and 2-(2-chlorophenylamino)-6-diethylamino-fluoran (Compound No. AE).
  • Heat sensitive record sheets No. a to No. ab and comparative sheets No. ac, No. ad and No. ae were heated at a temperature of 150°C for 5 seconds, whereby the developed color hue, the developed color density and the initial color density were measured by means of Macbeth reflex densitometer RD-514 model with a black filter (Wratten # 106).
  • Heat sensitive record sheets No. a to No. ab and comparative sheets No. ac, No. ad and No. ae were heated for color-development within the temperature range of from 70 to 160°C for 5 seconds, whereby the color density at each temperature was measured in the same manner as in the above test (1), and the color-development initiation temperature and the rising for the color-development were calculated from the relationship between the temperature and the color density.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Color Printing (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  • The present invention relates to novel fluoran compounds. More particularly, the invention relates to 2- substituted amino-3-alkoxy-6-di-substituted aminofluoran compounds which are useful as color precursors for heat sensitive record sheets or electrical heat sensitive record sheets.
  • European Patent 0 005 379 discloses in Example E a fluoran compound having an alkoxy group of the 3-position. FR-A-2 230 632 discloses a wide range of fluoran compounds and heat sensitive recording sheets, therein and fluoran compounds are used.
  • Certain fluoran compounds have been disclosed in Japanese Examined Patent Publications No. 2406/ 1973, No. 43296/1973, No. 32767/1974 and No. 23204/1976, and Japanese Unexamined Patent Publication No. 34526/1974. These fluoran compounds are used as color precursors for heat sensitive record sheets or electrical heat sensitive record sheets. However, heat sensitive record sheets wherein these fluoran compounds are used as color precursors, have various drawbacks, for instance, in the developed color density, the initial color density, the color-development initiation temperature and the gradient for color-development. Therefore, they cannot provide adequate properties required for heat sensitive record sheets. For instance, 2-anilino-3-methyl-6-diethylamino-fluoran disclosed in the above-mentioned Japanese Examined Patent Publications, tends to undergo partial color development during the preparation of heat sensitive record sheets, whereby the initial color density of the record sheets tends to be high. On the other hand, with a heat sensitive record sheet wherein 2-(2-chlorophenylamino)-6-diethylamino-fluoran is used, the initial color density is low, but the color-development initiation temperature is too high and the gradient for the color development is inadequate. Further, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylamino-fluoran does not provide an adequate gradient for color development.
  • The gradient for color-development means a rising of a curve in a diagram of color density-color development temperature curve given by plotting color densities on the ordinate and color-development temperatures on the abscissa as a value given by multiplying by 100 the value of tan 6 in the maximum slant of the curve.
  • The present inventors have conducted extensive researches for fluoran compounds to be used for heat sensitive record sheets which have no substantial self-color development, a high developed color density, a low color-development initiation temperature and a high gradient for color-development, and have finally found that 2-substituted amino-3-alkoxy-6-di-substituted aminofluoran compounds have excellent properties to satisfy the above requirements.
  • Namely, the present invention provides fluoran compounds represented by general formula:
    Figure imgb0001
    where each of R, and R2 is a C,-C4 alkyl group, a cyclohexyl group or an optionally substituted phenyl group as defined in claim 1, or R, and R2 may form together with N a saturated ring, R3 is a benzyl or phenyl group which may be substituted by a methyl group, an ethyl group or a halogen atom, and R4 is a Cl-C4 alkyl group, provided that when R, and R2 are ethyl and R3 is phenyl, R4 is not a methyl group.
  • The present invention also provides a heat sensitive record sheet which comprises a coated layer comprising a fluoran compound represented by the above general formula I.
  • Now the present invention will be described in detail with reference to the preferred embodiments.
  • The fluoran compounds represented by the general formula I according to the present invention are colorless or slightly colored solids which are stable in air and which, when brought in contact with an acidic substance, immediately form coloring agents having a dark black color. The developed coloring agents have excellent storage stability and are therefore quite useful.
  • The fluoran compounds represented by the general formula I according to the present invention may be prepared by following method (1), (2) or (3).
    • (1) An aniline derivative represented by the general formula:
      Figure imgb0002
      where R is a hydrogen atom or a C1―C4 alkyl group, and R3 and R4 are as defined above with respect to the ; general formula I, and a benzophenone compound represented by the general formula:
      Figure imgb0003
      where R, and R2 are as defined above with respect to the general formula I, are reacted in the presence of concentrated sulfuric acid at a temperature of from 0 to 80°C for several hours. After the reaction, the reaction mixture is poured into water and then adjusted to a pH of from 8 to 10 with an addition of sodium hydroxide, whereupon the precipitates are collected by filtration. To the cake thus obtained, toluene and an aqueous solution containing from 5 to 10% of sodium hydroxide are added, and the mixture is stirred for from 1 to 3 hours under reflux, whereupon the toluene layer is separated by liquid separation, washed with water and then concentrated. The precipitated crystals are collected by filtration. The crystals are dried, whereby a slightly colored 2-substituted amino-3-alkoxy-6-di-substituted amino-fluoran represented by the general formula I is obtainable in high purity and high yield. If necessary, the product is recrystallized from a volatile organic solvent such as toluene, acetone, butylacetate or hexane.
    • (2) A 2-amino-3-alkoxy-6-di-substituted amino-fluoran represented by the general formula:
      Figure imgb0004
      where R" R2 and R4 are defined above with respect to the general formula I, is reacted with a substituted benzyl chloride or a substituted benzyl bromide in a volatile organic inert solvent in the presence of an acid- binding agent such as sodiuim bicarbonate, or with a substituted bromobenzene or chlorobenzene in a volatile organic inert solvent in the presence of potassium carbonate by using copper power and iodine as catalysts, whereby a 2-substituted amino-3-alkoxy-6-di-substituted amino-fluoran represented by the general formula I is obtainable.
    • (3) A 2-substituted amino-3-hydroxy-6-di-substituted amino-fluoran represented by the general formula:
      Figure imgb0005
      where R1, R2 and R3 are as defined above with respect to the general formula I, is reacted with an alkylating agent such as dimethyl sulfate, methyl p-toluene sulfonate or methyl iodide in the presence of an alkali such as sodium hydroxide in water or in a volatile organic inert solvent, whereby a 2-substituted amino-3-alkoxy-6-di-substituted amino-fluoran represented by the general formula I is obtainable.
  • From the practical point of view, the method (1) is preferred.
  • As representative compounds of the above general formula I of the present invention, there may be mentioned 2 - benzylamino - 3 - methoxy - 6 - diethylamino-fluoran, 2 - benzylamino - 3 - methoxy - 6 - di - n - butylamino - fluoran, 2 - benzylamino - 3 - methoxy - 6 - N - methyl - N - cyclohexylamino - fluoran, 2 - anilino - 3 - methoxy - 6 - N - methyl - N - cyclohexylamino - fluoran, 2 - (2 - methylphenylamino) - 3 - methoxy - 6 - diethylamino - fluoran, 2 - (2 - methylphenylamino) - 3 - methoxy - 6 - di - n - butylamino - fluoran, 2 - (4 - methylphenylamino) - 3 - methoxy - 6 - diethylamino - fluoran, 2 - (4 - methylphenylamino) - 3 - methoxy - 6 - di - n - butylamino - fluoran, 2 - (2 - chlorophenylamino) - 3 - methoxy - 6 - diethylamino - fluoran, 2 - (2 - chlorophenylamino) - 3 - methoxy - 6 - di - n - butylamino - fluoran, 2 - (4 - chlorophenylamino) - 3 - methoxy - 6 - diethylamino. - fluoran, 2 - (4 - chlorophenylamino) - 3 - methoxy - 6 - di - n - butylamino - fluoran, 2 - anilino - 3 - ethoxy - 6 - diethylamino - fluoran, 2 - anilino - 3 - ethoxy - 6 - di - n - butylamino - fluoran, 2 - anilino - 3 - ethoxy - 6 - N - methyl - N - cyclohexylaminofluoran, 2 - anilino - 3 - ethoxy - 6 - N - ethyl - N - p - tolylamino - fluoran, 2 - (2 - methylphenylamino) - 3 - ethoxy - 6 - diethylamino - fluoran, 2 - (2 - methylphenylamino) - 3 - ethoxy - 6 - di - n - butylamino - fluoran, 2 - (4 - methylphenylamino) - 3 - ethoxy - 6 - diethylamino - fluoran, 2 - (4 - methylphenylamino) - 3 - ethoxy - 6 - di - n - butylamino - fluoran, 2 - (4 - methylphenylamino) - 3 - ethoxy - 6 - N - ethyl - N - p - tolylamino - fluoran, 2 - (4 - chlorophenylamino) - 3 - ethoxy - 6 - diethylamino - fluoran, 2 - (4 - chlorophenylamino) - 3 - ethoxy - 6 - di - n - butyl - fluoran, 2 - (4 - chlorophenylamino) - 3 - ethoxy - 6 - N - ethyl - N - p - tolylamino - fluoran, 2 - anilino - 3 - methoxy - 6 - pyrrolidinyl - fluoran, 2 - anilino - 3 - methoxy - 6 - N - ethyl - N - cyclohexylamino - fluoran, 2 - anilino - 3 - propoxy - 6 - diethylamino - fluoran, 2 - anilino - 3 - propoxy - 6 - di - n - butylamino - fluoran, 2 - anilino - 3 - butoxy - 6 - diethylamino - fluoran, 2 - anilino - 3 - butoxy - 6 - di - n - butylamino - fluoran.
  • As typical representatives of the aniline derivative represented by the general formula II to be used in the present invention, there may be mentioned N - benzyl - 2,4 - dimethoxyaniline, N - phenyl - 2,4 - dimethoxyaniline, N - (2 - methylphenyl) - 2,4 - dimethoxyaniline, N - (4 - methylphenyl) - 2,4 - dimethoxyaniline, N - (2 - chlorophenyl) - 2,4 - dimethoxyaniline, N - (4 - chlorophenyl) - 2,4 - dimethoxyaniline, N -benzyl -4 -hydroxy -2 -methoxyaniline, N -phenyl -4 -hydroxy -2 - methoxyaniline, N - phenyl - 2,4 - diethoxyaniline, N - (2 - methylphenyl) - 2,4 - diethoxyaniline, N - (4 - methylphenyl) - 2,4 - diethoxyaniline, N - (2 - chlorophenyl) - 2,4 - diethoxyaniline, N - (4 - chlorophenyl) - 2,4 - diethoxyaniline and N - phenyl - 4 - hydroxy - 2 - ethoxyaniline. Among the above aniline derivatives, those substituted by an alkoxy group at 4-position are preferred from the practical point of view.
  • As the benzophenone compound represented by the above general formula III to be used in the present invention, there may be mentioned 2 - hydroxy - 4 - dimethylamino - 2' - carboxybenzophenone, 2 - hydroxy - 4 - diethylamino - 2' - carboxybenzophenone, 2 - hydroxy - 4 - dipropylamino - 2' - carboxybenzophenone, 2 - hydroxy - 4 - dibutylamino - 2' - carboxybenzophenone, 2 - hydroxy - 4 - N - methyl - N - cyclohexylamino - 2' - carboxybenzophenone, 2 - hydroxy - 4 - N - ethyl - N - p - tolylamino - 2' - carboxy - benzophenone, 2 - hydroxy - 4 - pyrrolidinyl - 2' - carboxybenzophenone and 2 - hydroxy - 4 - piperidino - 2' - carboxy - benzophenone.
  • As representatives of the 2 - amino - 3 - alkoxy - 6 - disubstituted amino-fluoran represented by the above general formula IV to be used in the present invention, there may be mentioned 2 - amino - 3 - methoxy - 6 - dimethylamino - fluoran, 2 - amino - 3 - methoxy - 6 - diethylamino - fluoran, 2 - amino - 3 - methoxy - 6 - dipropylamino - fluoran, 2 - amino - 3 - methoxy - 6 - dibutylamino - fluoran, 2 - amino - 3 - methoxy - 6 - N - methyl - N - cyclohexylamino - fluran, 2 - amino - 3 - methoxy - 6 - N - ethyl - N - p - tolylamino - fluoran, 2 - amino - 3 - methoxy - 6 - pyrrolidinyl - fluoran, 2 - amino - 3 - methoxy - 6 - piperidino fluoran, 2 - amino - 3 - ethoxy - 6 - dimethylamino - fluoran, 2 -amino -3 - ethoxy -6 - diethylamino fluoran, 2 - amino - 3 - propoxy - 6 dipropylamino- fluoran, 2 - amino - 3 - propoxy - 6 - dibutylamino - fluoran, 2 - amino - 3 - butoxy - 6 - N - methyl - N - cyclohexylamino - fluoran and 2 - amino - 3 - butoxy - 6 - N - ethyl - N - p - tolylamino - fluoran.
  • As representatives of the 2 - substituted amino - 3 - hydroxy - 6 - di - substituted amino - fluoran represented by the above general formula V to be used in the present invention, there may be mentioned 2 - benzylamino - 3 - hydroxy - 6 - diethylamino - fluoran, 2 - anilino - 3 - hydroxy - 6 - dimethylamino - fluoran, 2 - anilino - 3 - hydroxy - 6 - diethylamino - fluoran, 2 - anilino - 3 - hydroxy - 6 - di- propylaminofluoran, 2 - anilino 3 - hydroxy - 6 - dibutylamino - fluoran, 2 - anilino - 3 - hydroxy - 6 - N - methyl - N - cyclohexylamino - fluoran, 2 - anilino - 3 - hydroxy - 6 - N - ethyl - N - p - tolylamino - fluoran, 2 - (4 - methylphenylamino) - 3 - hydroxy - 6 - diethylamino - fluoran, 2 - (2 - methylphenylamino) - 3 - hydroxy - 6 - diethylamino fluoran, 2 - (4 - chlorophenylamino) - 3 - hydroxy - 6 - diethylamino - fluoran and 2 - (2 - chlorophenylamino) - 3 - hydroxy - 6 - diethylaminofluoran.
  • As the substituted benzylchloride or the substituted benzyl bromide to be used in the present invention, there may be mentioned benzylchloride, benzylbromide, 2-chlorobenzylchloride, 2-chlorobenzylbromide, 3-chlorobenzylchloride, 4-chlorobenzylchloride, 2-methylbenzylchloride, 4-methylbenzylchloride, 3-methylbenzylchloride and 2-methylbenzylbromide.
  • As the substituted bromobenzene or substituted chlorobenzene to be used in the present invention, there may be mentioned 2-bromochlorobenzene, o-dichlorobenzene, 3-bromochlorobenzene, 4-bromochlorobenzene, bromobenzene, 2-bromotoluene, 4-bromotoluene or 3-bromotoluene.
  • As the condensing agent to be used in the present invention, there may be mentioned concentrated sulfuric acid, acetic acid anhydride, phosphoric acid, polyphosphoric acid, phosphorus oxychloride and zinc chloride. From the practical point of view, it is preferred to use concentrated sulfuric acid which serves as a solvent for a benzophenone compound represented by the above general formula III and at the same time serves as a condensing agent.
  • Now, the present invention will be described in further detail with reference to Examples for the preparation of typical 2-substituted amino-3-alkoxy-6-di-substituted amino-fluoran compounds of the present invention and Application Examples.
    • Example 1 2-Benzylamino-3-methoxy-6-diethyl-fluoran (Compound No. A)
  • To 150 g of 95% sulfuric acid, 12.5 g of 2-hydroxy-4-diethylamino-2'-carboxy-benzophenone was added and completely dissolved at a temperature of about 20°C, and then 9.7 g of N-benzyl-2,4-dimethoxyaniline was added and reacted therewith at a temperature of from 10 to 20°C for 24 hours. After the reaction, the reaction mixture was poured into 1 liter of ice water and then adjusted to a pH of from 7 to 8 by an addition of 10% sodium hydroxide aqueous solution, whereupon the precipitates were collected by filtration. To the cake thus obtained, 300 ml of toluene and 150 ml of a 10% sodium hydroxide aqueous solution were added, and the mixture was stirred for 2 hours under reflux. Then, the toluene layer was separated by liquid separation, then washed with water, concentrated to dryness and solidified by an addition of hexane. The solid thereby obtained was dried to obtain 20.5 g of slightly pink 2-benzylamino-3-methoxy-6-diethylaminofluoran. The melting point of this product was from 72 to 76°C. Further, this product had Àmax at 439 nm (a molecular extinction coefficient (hereinafter referred to simply as "MEC"): 1.42 x 104) and at 583 nm (MEC: 3.91 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
  • The N-benzyl-2,4-dimethoxyaniline used as a starting material was prepared in the following manner.
  • Into 150 ml of ethanol, 30.6 g of 2,4-dimethoxyaniline and 21.2 g of benzaldehyde were dissolved, and 2 g of acetic acid was added. The mixture was reacted at a temperature of from 50 to 60°C for 4 hours. The reaction solution was poured into 500 ml of water and extracted with 300 ml of toluene. The toluene solution was separated by liquid separation, then washed with water and concentrated to dryness. The oily product thereby obtained was dissolved into 150 ml of ethanol, and 11.3 g of sodium boro-hydride was added in 2 hours at a temperature of from 30 to 40°C and reacted therewith. Further, the mixture was stirred for one hour at a temperature of 40°C. The reaction mixture was poured into 1 liter of water and extracted with 500 m of toluene. The toluene layer was washed with water, concentrated and purified by distillation under reduced pressure, whereby 40.9 g of N-benzyl-2,4-dimethoxyaniline was obtained. The product was a liquid having a boiling point of from 166 to 168°C 266 PLa (2 mmHg).
    • Example 2 2-Benzylamino-3-methoxy-6-di-n-butylamino-fluoran (Compound No. B)
  • To 70 g of 95% sulfuric acid, 7.4 g of 2-hydroxy-4-di-n-butylamino-2'-carboxy-benzophenone and 4.9 g of N-benzyl-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1, whereby 9.8 g of slightly purple 2-benzylamino-3-methoxy-6-di-n-butylamino-fluoran was obtained. The melting point of this product was from 134 to 136°C. The product had λmax at 443 nm (MEC: 1.59 x 104) and at 587 nm (MEC: 3.95 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned blackish purple.
    • Example 3 2-Benzylamino-3-methoxy-6-N-methyl-N-cyclohexylaminofluoran (Compound No. C)
  • To 70 g of 95% sulfuric acid, 7.1 g of 2-hydroxy-4-N-methyl-N-cyclohexylamino-2'-carboxybenzophenone and 4.9 g of N-benzyl-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystallized from toluene, whereby 8.3 g of slightly purple 2-benzyl-3-methoxy-6-N-methyl-N-cyclohexylaminofluoran was obtained. The melting point of this product was from 210 to 211.5°C. The product had λmax at 443 nm (MEC: 1.55 x 104) and at 587 nm (MEC: 3.94 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned blackish purple.
    • Example 4 2-Anilino-3-methoxy-6-di-n-butylamino-fluoran (Compound No. E)
  • To 150 g of 95% sulfuric acid, 18.5 g of 2-hydroxy-4-di-n-butylamino-2'-carboxy-benzophenone and 11.5 g of N-phenyl-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystallized from toluene, whereby 20.9 g of white 2-anilino-3-methoxy-6-di-n-butylamino- fluoran was obtained. The melting point of this product was from 169 to 172°C. The product had λmax at 451 nm (MEC; 1.52 x 104) and at 593 nm (MEC: 3.29 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
    • Example 5 2-Anilino-3-methoxy-6-N-methyl-N-cyclohexylaminofluoran (Compound No. F)
  • To 60 g of 95% sulfuric acid, 7.1 g of 2-hydroxy-4-N-methyl-N-cyclohexylamino-2'-carboxybenzophenone and 4.6 g of N-phenyl-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystallized from acetone, whereby 4.4 g of white 2-anilino-3-methoxy-6-N-methyl-N-cyclohexylamino-fluoran was obtained. The melting point of this product was from 201 to 203.5°C. The product had Àmax at 450 nm (MEC: 1.63 x 104) and at 593 nm (MEC: 3.45 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish-black.
    • Example 6 2-Anilino-3-methoxy-6-N-ethyl-N-p-tolylamino-fluoran (Compound No. G)
  • To 60 g of 95% sulfuric acid, 7.5 g of 2-hydroxy-4-N-ethyl-N-p-tolylamino-2'-carboxy-benzophenone and 4.6 g of N-phenyl-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystalized from toluene, whereby 6.8 g of white 2-anilino-3-methoxy-6-N-ethyl-N-p-tolylamino-fluoran was obtained. The melting point of this product was from 196 to 199°C. The product had Àmax at 453 nm (MEC: 1.82 x 104) and at 595 nm (MEC: 3.19 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
    • Example 7 2-(2-Metylphenylamino)-3-methoxy-6-diethylaminofluoran (Compound No. H)
  • To 150 g of 95% sulfuric acid, 15.7 g of 2-hydroxy-4-diethylamino-2'-carboxy-benzophenone and 12.2 g of N-(2-methylphenyl)-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystallized from toluene, whereby 18.7 g of white 2-(2-methylanilino)-3-methoxy-6-diethylamino-fluoran was obtained. The melting point of this product was from 124 to 127°C. The product had Àmax at 441 nm (MEC: 1.40 x 104) and at 586 nm (MEC: 3.18 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
  • The N-(2-methylphenyl)-2,4-dimethoxyaniline used as a starting material was prepared in the same manner as in Example 4 by using N-acetyl-2,4-dimethoxyaniline and 2-bromotoluene as the starting materials. The boiling point of the N-(2-methylphenyl)-2,4-dimethoxyaniline was from 172 to 175°C/266 Pa (2 mmHg).
    • Example 8 2-(2-Methylphenylamino)-3-methoxy-6-di-n-butylaminofluoran (Compound No. I)
  • To 150 g of 95% sulfuric acid, 18.5 g of 2-hydroxy-4-di-n-butylamino-2'-carboxy-benzophenone and 12.2 g of N-(2-methylphenyl)-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystallized from toluene, whereby 18.3 g of white 2-(2-methylphenylamino)-3-methoxy-6-di-n-butylamino-fluoran was obtained. The melting point of this product was from 139 to 142°C. The product had Àmax at 444 nm (MEC: 1.57 x 104) and at 588 nm (MEC: 3.64 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
    • Example 9 2-(4-Methylphenylamino)-3-methoxy-6-diethylaminofluoran (Compound No. J)
  • To 150 g of 95% sulfuric acid, 15.7 g of 2-hydroxy-4-diethylamino-2'-carboxy-benzophenone and 12.2 g of N-(4-methylphenyl)-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystallized from acetone, whereby 22.3 g of white 2-(4-methylphenylamino)-3-methoxy-6-diethylamino-fluoran was obtained. The melting point of this product was from 141 to 145°C. The product had λmax at 453 nm (MEC: 1.40 x 104) and at 595 nm (MEC: 2.58 x 104) as measured in 95% aceticacid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned black.
  • The N-(4-methylphenyl)-2,4-dimethoxyaniline used as a starting material was prepared in the same manner as in Example 4 by using N-acetyl-2,4-dimethoxyaniline and 4-bromotoluene as the starting materials. The boiling point of the N-(4-methylphenyl)-2,4-dimethoxyaniline was from 173 to 175°C/266 Pa (2 mmHg).
    • Example 10 2-(4-Methylphenylamino)-3-methoxy-6-di-n-butylaminofluoran (Compound No. K)
  • To 150 g of 95% sulfuric acid, 18.5 g of 2-hydroxy-4-di-n-butylamino-2'-carboxy-benzophenone and 12.2 g of N-(4-methylphenyl)-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystallized from toluene, whereby 15.6 g of white 2-(4-methylphenylamino)-3-methoxy-6-di-n-butylamino-fluoran was obtained. The melting point of this product was from 106 to 109°C. The product had λmax at 455 nm (MEC: 1.65 x 104) and at 600 nm (MEC: 3.14 x 104) as measured in 95% acetics acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
    • Example 11 2-(2-Chlorophenylamino)-3-methoxy-6-diethylaminofluoran (Compound No. L)
  • To 150 g of 95% sulfuric acid, 15.7 g of 2-hydroxy-4-diethylamino-2'-carboxy-benzophenone and 13.2 g of N-(2-chlorophenyl)-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystallized from toluene, whereby 13.4 g of white 2-(4-chlorophenylamino)-3-methoxy-6-diethylamino-fluoran was obtained. The melting point of this product was from 121 to 125°C. The product had λmax at 437 nm (MEC: 1.29 x 104) and at 577 nm (MEC: 3.63 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned dark red.
  • The N-(2-chlorophenyl)-2,4-dimethoxyaniline used as a starting material was prepared in the same manner as in Example 4 by using N-acetyl-2,4-dimethoxyaniline and 2-bromochlorobenzene as the starting materials. The N-(2-chlorophenyl)-2,4-dimethoxyaniline was an oil having a boiling point of from 170 to 177°C/266 Pa (2 mmHg).
    • Example 12 2-(2-Chlorophenylamino)-3-methoxy-6-di-n-butylaminofluoran (Compound No. M)
  • To 125 g of 95% sulfuric acid, 14.8 g of 2-hydroxy-4-di-n-butylamino-2'-carboxy-benzophenone and 10.6 g of N-(2-chlorophenyl)-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystallized from toluene, whereby 12.2 g of white 2-(2-chlorophenylamino)-3-methoxy-6-di-n-butylamino-fluoran was obtained. The melting point of this product was from 105 to 107°C. The product had λmax at 440 nm (MEC: 1.30 x 104) and at 580 nm (MEC: 3.78 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned dark red.
    • Example 13 2-(4-Chlorophenylamino)-3-methoxy-6-diethylaminofluoran (Compound No. N)
  • To 150 g of 95% sulfuric acid, 15.7 g of 2-hydroxy-4-diethylamino-2'-carboxy-benzophenone and 13.2 g of N-(4-chlorophenyl)-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystallized from toluene, whereby 20.7 g of white 2-(4-chlorophenylamino)-3-methoxy-6-diethylamino-fluoran was obtained. The melting point of this product was from 123 to 127°C. The product had Àmax at 449 nm (MEC: 1.34 x 104) and at 587 nm (MEC: 2.95 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
  • The N-(4-chlorophenyl)-2,4-dimethoxyaniline used as a starting material was prepared in the same manner as in Example 4 by using N-acetyl-2,4-dimethoxyaniline and 4-bromochlorobenzene as the starting materials. The N-(4-chlorophenyl)-2,4-dimethoxyaniline was an oil having a boiling point of from 178 to 180°C/266 Pa (2 mmHg).
    • Example 14 2-(4-Chlorophenylamino)-3-methoxy-6-di-n-butylaminofluoran (Compound No. O)
  • To 150 g of 95% sulfuric acid, 18.5 g of 2-hydroxy-4-di-n-butylamino-2'-carboxy-benzophenone and 13.2 g of N-(4-chlorophenyl)-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The product was recrystallized from toluene, whereby 18.0 g of white 2-(4-chlorophenylamino)-3-methoxy-6-di-n-butylamino-fluoran was obtained. The melting point of this product was from 91 to 95°C. The product had Àmax at 449 nm (MEC: 1.46 x 104) and at 590 nm (MEC: 3.36 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
    • Example 15 2-Anilino-3-ethoxy-6-diethylamino-fluoran (Compound No. P)
  • To 100 g of 95% sulfuric acid, 9.4 g of 2-hydroxy-4-diethylamino-2'-carboxy-benzophenone was added and completely dissolved at a temperature of about 20°C, and then 7.7 g of N-phenyl-2,4-diethoxyaniline was added and reacted therewith at a temperature from 10 to 20°C for 24 hours. After the reaction, the reaction mixture was poured into 700 ml of ice water and adjusted to pH of from 7 to 8 by an addition of a 10% sodium hydroxide aqueous solution, whereupon the precipitates were collected by filtration. To the cake thereby obtained, 300 ml of toluene and 150 ml of a 10% sodium hydroxide aqueous solution were added, and the mixture was stirred for 2 hours under reflux. Then, the toluene layer was separated by liquid separation, washed with water, concentrated to dryness and solidified by an addition of hexane. The solidified product was dried to obtain 12.1 g of slightly pink 2-anilino-3-ethoxy-6-diethylamino-fluoran. The melting point of this product was from 84 to 88°C. The product had Àmax at 452 nm (MEC: 1.44 x 104) and at 593 nm (MEC: 2.93 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact in which silica gel, the product readily underwent color-development and turned bluish black.
  • The N-phenyl-2,4-diethoxyaniline used as starting material was prepared in the following manner.
  • To a mixture of 66.9 g of N-acetyl-2,4-diethoxyaniline and 70.7 g of bromobenzene, 29 g of anhydrous potassium carbonate, 2.1 g of copper powder and 0.8 g of iodine were added, and the mixture was reacted at a temperature of from 170 to 180°C for 20 hours. Then, to this reaction mixture, 30 g of potassium hydroxide and 100 ml of isoamylalcohol were added, and the mixture was reacted at a temperature from 120 to 130°C for 3 hours. Then, 300 ml of toluene was added thereto. The toluene layer was washed with water, separated by liquid separation, concentrated and then purified by distillation under reduced pressure, whereby 54 g of oily N-phenyl-2,4-di-ethoxyaniline was obtained. The boiling point of this product was from 180 to 185°C/399 Pa (3 mmHg).
    • Example 16 2-Anilino-3-ethoxy-6-di-n-butylamino-fluoran (Compound No. Q)
  • To 100 g of 95% sulfuric acid, 11.1 g of 2-hydroxy-4-di-n-butylamino-2'-carboxy-benzophenone and 7.7 g of N-phenyl-2,4-diethoxyaniline were added and reacted in the same manner as in Example 16. The product was recrystallized from cyclohexene, whereby 11.8 g of white 2-anilino-3-ethoxy-6-di-n-butylamino-fluoran was obtained. The melting point of this product was from 125 to 128°C. The product had λmax at 453 nm (MEC: 1.48 x 104) and at 597 nm (MEC: 3.17 x 10°) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
    • Example 17 2-Anilino-3-ethoxy-6-N-methyl-N-cyclohexylaminofluoran (Compound No. R)
  • To 100 g of 95% sulfuric acid, 10.6 g of 2-hydroxy-4-N-methyl-N-cyclohexylamino-2'-carboxybenzophenone and 7.7 g of N-phenyl-2,4-diethoxyaniline were added and reacted in the same manner as in Example 16. The product was recrystallized from n-octylchloride, whereby 9.0 g of white 2-anilino-3- ethoxy-6-N-methyl-N-cyclohexylaminofluoran was obtained. The melting point of this product was from 169 to 173°C. The product had Åmax at 452 nm (MEC: 1.47 x 104) and at 597 nm (MEC: 3.16 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
    • Example 18 2-Anilino-3-ethoxy-6-N-ethyl-N-p-tolylaminofluoran (Compound No. S)
  • To 100 g of 95% sulfuric acid, 11.3 g of 2-hydroxy-4-N-ethyl-N-p-tolylamino-2'-carboxy-benzophenone and 7.7 g of N-phenyl-2,4-diethoxyaniline were added and reacted in the same manner as in Example 16. The product was recrystallized from n-butylchloride, whereby 12.7 g of white 2-anilino-3-ethoxy-6-N-ethyl-N-p-tolylamino-fluoran was obtained. The melting point of this product was from 148 to 152°C. The product had λmaX at 453 nm (MEC: 1.92 x 104) and at 595 nm (MEC: 3.42 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
    • Example 19 2-(2-Methylphenylamino)-3-ethoxy-6-diethylaminofluoran (Compound No. T)
  • To 75 g of 95% sulfuric acid, 6.9 g of 2-hydroxy-4-diethylamino-2'-carboxy-benzophenone and 5.4 g of N-(2-methylphenyl)-2,4-diethoxyaniline were added and reacted in the same manner as in Example 16. The product was recrystallized, whereby 7.8 g of white 2-(2-methylphenylamino)-3-ethoxy-6-diethylamino- fluoran was obtained. The melting point of this product was from 197.5 to 200°C. The product had λmax at 443 nm (MEC: 1.46 x 104) and at 586 nm (MEC: 3.46 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
  • The N-(2-methylphenyl)-2,3-diethoxyaniline used as a starting material was prepared in the same manner as in Example 16 by using N-acetyl-2,4-diethoxyaniline and 2-bromotoluene as the starting materials. The boiling point of the N-(2-methylphenyl)-2,4-diethoxyaniline was from 170 to 172°C/67 Pa (0.5 mmHg).
    • Example 20 2-(2-Methylphenylamino)-3-ethoxy-6-di-n-butylaminofluoran (Compound No. U)
  • To 75 g of 95% sulfuric acid, 8.1 g of 2-hydroxy-4-di-n-butylamino-2'-carboxy-benzophenone and 5.4 g of N-(2-methylphenyl)-2,4-diethoxyaniline were added and reacted in the same manner as in Example 16. The product was recrystallized, whereby 8.1 g of white (2-(2-methylphenylamino)-3-ethoxy-6-di-n-butylamino-fluoran was obtained. The melting point of this product was from 125 to 130°C. The product had Åmax at 444 nm (MEC: 1.49 x 104) and at 589 nm (MEC: 3.63 x 104) as measured in 95% acetic acid. A. solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
    • Example 21 2-(4-Methylphenylamino)-3-ethoxy-6-diethylaminofluoran (Compound No. V)
  • To 100 g of 95% sulfuric acid, 10.3 g of 2-hydroxy-4-diethylamino-2'-carboxy-benzophenone and 8.1 g of N-(4-methylphenyl)-2,4-diethoxyaniline were added and reacted in the same manner as in Example 16. The product was recrystallizd, whereby 11.7 g of white 2-(4-methylphenylamino)-3-ethoxy-6-diethylamino- fluoran was obtained. The melting point of this product was from 110 to 113°C. The product had Åmax at 454 nm (MEC: 1.47 x 104) and at 597 nm (MEC: 2.85 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
  • The N-(4-methylphenyl)-2,4-diethoxyaniline used as a starting material was prepared in the same manner as in Example 16 by using N-acetyl-2,4-diethoxyaniline and 4-bromotoluene as the starting materials. The boiling point of the N-(4-methylphenyl)-2,4-diethoxyaniline was from 195 to 197°C/399 Pa (3 mmHg).
    • Example 22 2-(4-Methylphenylamino)-3-ethoxy-6-di-n-butylaminofluoran (Compound No. W)
  • To 100 g of 95% sulfuric acid, 12.2 g of 2-hydroxy-4-di-n-butylamino-2'-carboxy-benzophenone and 8.1 g of N-(4-methylphenyl)-2,4-diethoxyaniline were added and reacted in the same manner as in Example 16. The product was recrystallized, whereby 11.4 g of slightly pink 2-(4-methylphenylammino)-3-ethoxy-6-di-n-butylamino-fluoran was obtained. The melting point of this product was from 137 to 141°C. The product had λmax at 454 nm (MEC: 1.57 x 104) and at 597 nm (MEC: 3.14 x 10°) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned purplish black.
    • Example 23 2-(4-Methylphenylamino)-3-ethoxy-6-N-ethyl-N-p-tolylamino-fluoran (Compound No. X)
  • To 100 g of 95% sulfuric acid, 12.3 g of 2-hydroxy-4-N-ethyl-N-p-tolylamino-2'-carboxy-benzophenone and 8.1 g of N-(4-methylphenyl)-2,4-diethoxyaniline were added and reacted in the same manner as in Example 16. The product was recrystallized from toluene, whereby 13.3 g of white 2-(4-methylphenylamino)-3-ethoxy-6-N-ethyl-N-p-tolylaminofluoran was obtained. The melting poing of this product was from 155 to 158°C. The product had λmax at 459 nm (MEC: 1.84 x 104) and at 601 nm (MEC: 2.92 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, and the product readily underwent color-development and turned greenish black.
    • Example 24 2-(4-Chlorophenylamino)-3-ethoxy-6-diethylaminofluoran (Compound No. Y)
  • To 100 g of 95% sulfuric acid, 9.4 g of2-hydroxy-4-diethyiamino-2'-carboxy-benzophenoneand8.8g g of N-(4-chlorophenyl)-2,4-diethoxyaniline were added and reacted in the same manner as in Example 16. The product was recrystallized, whereby 13.5 g of white 2-(4-chlorophenylamino)-3-ethoxy-6-diethylamino- fluoran was obtained. The melting point of this product was from 136 to 140°C. The product had λmax at 448 nm (MEC: 1.55 x 104) and at 589 nm (MEC: 3.50 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
  • The N-(4-chlorophenyl)-2,4-diethoxyaniline used as a starting material was prepared in the same manner as in Example 16 by using N-acetyl-2,4-diethoxyaniline and 4-bromochlorobenzene as the starting materials. The N-(4-chlorophenyl)-2,4-diethoxyaniline had a boiling point of from 188 to 190°C/67 Pa (0.5 mmHg).
    • Example 25 2-(4-Chlorophenylamino)-3-ethoxy-6-di-n-butylaminofluoran (Compound No. Z)
  • To 100 g of 95% sulfuric acid, 11.1 g of 2-hydroxy 4-di-n-butylamino-2'-carboxy-benzophenone and 8.8 g of N-(4-chlorophenyl)-2,4-diethoxyaniline were added and reacted in the same manner as in Example 16. The product was recrystallized, whereby 15.4 g of slightly pink 2-(4-chlorophenylamino)-3-ethoxy-6-di-n-butylamino-fluoran was obtained. The melting point of this product was from 116 to 120°C. The product had Àmax at 449 nm (MEC: 1.39 x 104) and at 590 nm (MEC: 3.48 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
    • Example 26 2-(4-Chlorophenylamino)-3-ethoxy-6-N-ethyl-N-p-tolylamino-fluoran (Compound No. AA)
  • To 100 g of 95% sulfuric acid, 12.3 g of 2-hydroxy-4-N-ethyl-N-p-tolylamino-2'-carboxy-benzophenone and 8.8 g of N-(4-chlorophenyl)-2,4-diethoxyaniline were added and reacted in the same manner as in Example 16. The product was recrystallized from toluene, whereby 13.5 g of white 2-(4-chlorophenylamino)-3-ethoxy-6-N-ethyl-N-p-tolylamino-fluoran was obtained. The melting point of this product was from 144 to 147.5°C. The product had λmax at 453 nm (MEC: 1.68 x 104) and at 593 nm (MEC: 3.33 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
    • Example 27 2-(4-Chlorophenylamino)-3-methoxy-6-N-ethyl-N-p-tolylamino-fluoran (Compound No. AB)
  • To 100 g of 95% sulfuric aicd, 12.4 g of 2-hydroxy-4-N-ethyl-N-p-tolylamino-2'-carboxy-benzophenone and 8.0 g of N-(4-chlorophenyl)-2,4-dimethoxyaniline were added and reacted in the same manner as in Example 1. The prodct was recrystallized from toluene, whereby 12.9 g of white 2-(4-chlorophenylamino)-3-methoxy-6-N-ethyl-N-p-tolylamino-fluoran was obtained. The melting point of this product was from 209 to 213°C. The product had Àmax at 454 nm (MEC: 1.66 x 104) and at 591 nm (MEC: 3.13 x 104) as measured in 95% acetic acid. A solution of this product in toluene was colorless. When brought in contact with silica gel, the product readily underwent color-development and turned bluish black.
    • Application Example 1
  • To 2.0 g of Compound A prepared in Example 1, 20 g of water and 20 g of an. aqueous solution containing 10% by weight of polyvinyl alcohol were added. The mixture was slowly dispersed and mixed in a ball mill at room temperature for 24 hours, whereby a colorless slurry was obtained wherein the particle size of the compound was about 3 pm. On the other hand, 7 g of bisphenol A was added to 10 g of water and 40 g of an aqueous solution containing 10% by weight of polyvinyl alcohol. The mixture was slowly dispersed and mixed in a ball mill at room temperature for 24 hours, whereby a slurry was obtained. The solid substance in the slurry had an average particle size of about 5 11m. Both slurries were mixed, and the mixture was uniformly dispersed and mixed at room temperature for 1 hour, whereby a slurry mixture was prepared. This slurry mixture was coated on one surface of a normal paper of 50 g/m2 by means of a wire bar coater (wound wire: 0.35 mm in diameter) in an amount of the coated compound being 1.5 g/m2 of the paper. The coated paper was dried in air at room temperature, whereby a heat sensitive record sheet having a substantially colorless heat sensitive layer was obtained. This heat sensitive record sheet will be referred to as No. a.
  • In the same manner, heat sensitive record sheets No. b to No. o were prepared by using Compounds No. B to No. O.
    • Application Example 2
  • To 2.0 g of Compound No. P prepared in Example 16, 20 g of water and 20 g of an aqueous solution containing 10% by weight of polyvinyl alcohol were added. The mixture was slowly dispersed and mixed in a ball mill at room temperature for 24 hours, whereby a colorless slurry was obtained wherein the particle size of the compound was about 3 µm. On the other hand, 7 g of bisphenol A was added to 10 g of water and 40 g of an aqueous solution containing 10% by weight of polyvinyl alcohol. The mixture was slowly dispersed and mixed in a ball mill at room temperature for 24 hour, whereby a slurry was obtained. The solid substance in the slurry had an average particle size of about 5 11m. Both slurries were mixed, and the mixture was uniformly dispersed and mixed at room temperature for 1 hour, whereby a slurry mixture was prepared. This slurry mixture was coated on one surface of a normal paper of 50 g/m2 by means of a wire bar coater (wound wire: 0.35 mm in diameter) in an amount of the coated compound being 1.5 g/m2 of the paper. The coated paper was dried in air at room temperature, whereby a heat sensitive record sheet having a substantially colorless heat sensitive layer was obtained. This heat sensitive record sheet will be referred to as No. p.
  • In the same manner, heat sensitive record sheets No. q to No. ab were prepared by using Compounds No. Q to No. AB.
  • Further, for purpose of comparison, heat sensitive record sheets No. ac, No. ad and No. ae were prepared in the same manner as above by using known 2-anilino-3-methyl-6-diethylamino-fluoran (Compound No. AC) 2-anilino-3-methyl-6-N-methyl-N-cyclohexylamino-fluoran (Compound No. AD) and 2-(2-chlorophenylamino)-6-diethylamino-fluoran (Compound No. AE).
  • These heat sensitive record sheets were subjected to the following tests.
    • (1) Color-development performance test
  • Heat sensitive record sheets No. a to No. ab and comparative sheets No. ac, No. ad and No. ae were heated at a temperature of 150°C for 5 seconds, whereby the developed color hue, the developed color density and the initial color density were measured by means of Macbeth reflex densitometer RD-514 model with a black filter (Wratten # 106).
    • (2) Color-development characteristic test
  • Heat sensitive record sheets No. a to No. ab and comparative sheets No. ac, No. ad and No. ae were heated for color-development within the temperature range of from 70 to 160°C for 5 seconds, whereby the color density at each temperature was measured in the same manner as in the above test (1), and the color-development initiation temperature and the rising for the color-development were calculated from the relationship between the temperature and the color density.
  • The results of the above-mentioned color-development performance test (1) and the results of the measurement of the color-development values (2) are shown in the following Table.
    Figure imgb0006
    Figure imgb0007
  • It is evident from the results shown in the above Table that the heat sensitive record sheets wherein the fluoran compounds of the present invention are used, are far superior in the color-development performance and the developed color characteristics to the comparative heat sensitive record sheets wherein comparative fluoran compounds are used. Thus, the industrial value for practical application of the present invention is considerably high.

Claims (10)

1. A fluoran compound represented by general formula:
Figure imgb0008
where each of R, and R2 is a C1―C4 alkyl group, a cyclohexyl group or a phenyl group which may be substituted by a methyl group, an ethyl grop or a halogen atom, or R, and R2 may form together with N a saturated ring, R3 is a benzyl or a phenyl group which may be substituted by a methyl group, an ethyl group or a halogen atom, and R4 is a C1―C4 alkyl group, provided that when R1 and R2 are ethyl and R3 is phenyl, R4 is not a methyl group.
2. The fluoran compound according to claim 1, wherein R4 is a methyl group or an ethyl group.
The fluoran compound according to claim 2, wherein each of R, and R2 is an ethyl group, a propyl group or a butyl group.
4. The fluoran compound according to claim 1, which is 2-anilino-3-methoxy-6-di-n-butylamino- fluoran.
5. The fluoran compound according to claim 1, which is 2-anilino-3-methoxy-6-N-ethyl-N-p-tolylamino- fluoran.
6. The fluoran compound according to claim 1, which is 2-(2-chlorophenylamino)-3-methoxy-6-di-n-butylaminofluoran.
7. The fluoran compound according to claim 1, which is 2-anilino-3-ethoxy-6-di-N-butylamino-fluoran.
8. The fluoran compound according to claim 1, which is 2-anilino-3-ethoxy-6-N-methyl-N-cyclohexylamino-fluoran.
9. The fluoran compound according to claim 1, which is 2-anilino-3-ethoxy-6-N-ethyl-N-p-tolylamino- fluoran.
10. A heat sensitive record sheet which comprises a coated layer comprising a fluoran compound according to claim 1.
EP83109287A 1982-10-01 1983-09-19 Fluoran compounds Expired EP0107780B1 (en)

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JP17103982A JPS5962666A (en) 1982-10-01 1982-10-01 Fluoran compounds
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JP809483A JPS59135254A (en) 1983-01-22 1983-01-22 Fluoran compound

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US4629800A (en) * 1984-03-09 1986-12-16 Kanzaki Paper Manufacturing Co., Ltd. Fluoran compounds
CA1280433C (en) * 1985-10-08 1991-02-19 Teijiro Kitao Fluoran derivatives, process for preparation thereof and recording material containing the same
US8372782B2 (en) 2003-02-28 2013-02-12 Zink Imaging, Inc. Imaging system
US7704667B2 (en) 2003-02-28 2010-04-27 Zink Imaging, Inc. Dyes and use thereof in imaging members and methods
WO2004078874A2 (en) 2003-02-28 2004-09-16 Polaroid Corporation Novel dye complexes and use thereof in imaging members and methods
EP1879876A4 (en) 2005-05-12 2009-03-18 Zink Imaging Llc Novel rhodamine dyes
US7807607B2 (en) 2006-05-12 2010-10-05 Zink Imaging, Inc. Color-forming compounds and use thereof in imaging members and methods

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GB1192938A (en) * 1966-11-18 1970-05-28 Fuji Photo Film Co Ltd Improvements in or relating to Pressure-Sensitive Copying Paper
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CA1153610A (en) * 1978-05-09 1983-09-13 Edward J. Reardon, Jr. Carbonylic halides as activators for phototropic compositions
US4341403A (en) * 1979-04-24 1982-07-27 Fuji Photo Film Co., Ltd. Fluoran compounds, process for preparation thereof, and recording sheets using same
JPS57116685A (en) * 1981-01-12 1982-07-20 Sumitomo Chem Co Ltd Recording paper
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JPS5898281A (en) * 1981-12-08 1983-06-11 Jujo Paper Co Ltd Pressure-sensitive duplicate sheet
US4482905A (en) * 1982-08-31 1984-11-13 Hodogaya Chemical Co., Ltd. Heat sensitive record material

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